JPH1134254A - Manufacturing method of laminate - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To reduce the influence of bleeding of oils and fats contained in an olefin-based thermoplastic elastomer, thereby eliminating the need for a degreasing step or a primer coating step, and achieving excellent adhesion and scratch resistance. And a method for producing a laminate having the following. SOLUTION: One of the adhesive resin layers formed on the adhesive resin layer side or both surfaces of the obtained co-extruded sheet is formed by extruding an adhesive resin layer on one or both surfaces of a base material layer. Is coated with at least one selected from a saturated polyester resin, an acrylate resin and an isocyanate resin to form a skin layer, and a foam made of a thermoplastic resin is heat-fused on the surface opposite to the skin layer. At the same time, the skin layer side is embossed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an automobile interior material,
The present invention relates to a method for manufacturing a laminate used for stationery, interior and exterior materials of bags, building materials for interiors, and the like, and more particularly to a method for manufacturing a laminate having excellent surface properties as a skin material.

[0002]

2. Description of the Related Art Conventionally, as a laminate having excellent surface properties as a skin material, for example, soft polyvinyl chloride having an embossed surface or a blend of soft polyvinyl chloride and an ABS resin has been mainly used. Was. However, those using such polyvinyl chloride pollute the environment by hydrogen chloride gas generated during combustion.
There were problems such as fogging of the window glass due to volatilization of the plasticizer.

[0003] For this reason, it has been proposed to use, for example, a laminate of an olefin-based thermoplastic elastomer for such an application (Japanese Patent Publication No. 1-14023). However, the olefin-based thermoplastic elastomer has a defect in abrasion resistance. In order to improve such disadvantages, there has been proposed an olefin-based thermoplastic elastomer having a surface treated with a primer and further having a top coat layer formed thereon (Japanese Patent Application Laid-Open No. 63-272547).

However, when an olefin-based thermoplastic elastomer is produced, a mineral oil-based softener, which is considered to have a role as a processability improver, is used. Therefore, pretreatment such as degreasing is performed before primer treatment. And it is necessary to control the pot life and the like after the degreasing treatment. In addition, even if the corona treatment is performed, there is a problem that a sufficient primer effect cannot be obtained due to the bleeding of the oil and fat of the olefin-based thermoplastic elastomer.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to reduce the influence of bleeding of oils and fats contained in an olefin-based thermoplastic elastomer, thereby achieving excellent adhesion without the need for a degreasing step or a primer coating step. An object of the present invention is to provide a method for producing a laminate having properties and abrasion resistance.

[0006]

According to a first aspect of the present invention, there is provided a method for producing a laminate comprising a substrate comprising an adhesive resin layer and an olefin-based thermoplastic elastomer resin. Layer and co-extruded so as to form an adhesive resin layer on one or both surfaces of the base material layer, and the resulting co-extruded sheet may have any of the adhesive resin layers formed on the adhesive resin layer side or both surfaces. On the other hand, one or more selected from a saturated polyester resin, an acrylate resin and an isocyanate resin are applied to form a skin layer, and a foam made of a thermoplastic resin is heated on the surface opposite to the skin layer. In addition to the fusion, the skin layer side is embossed.

The invention according to claim 2 of the present invention (hereinafter referred to as “second
The method for producing a laminate according to the present invention is a method of forming an adhesive resin layer and a base layer made of an olefin-based thermoplastic elastomer resin such that an adhesive resin layer is formed on one or both sides of the base layer. A foam made of a thermoplastic resin is heat-sealed to one of the adhesive resin layers formed on the base layer side or both surfaces of the molten co-extruded sheet immediately after being extruded, and the unlaminated adhesive resin layer side The embossed surface is coated with at least one selected from a saturated polyester resin, an acrylate resin and an isocyanate resin to form a skin layer on the embossed surface.

Hereinafter, the first invention will be described. In the production method of the first invention, first, an adhesive resin layer is formed on one or both sides of the base material layer by co-extrusion to obtain a co-extruded sheet.

The substrate layer used in the first invention is formed from an olefin-based thermoplastic elastomer resin. As the olefin-based thermoplastic elastomer resin, for example, contains polypropylene as a hard segment,
Those containing ethylene as the soft segment (E
PM); those containing a small amount of a diene component together with ethylene (EPDM); blends of EPM and EPDM; those partially crosslinked by adding an organic peroxide (described in JP-B-1-14023); Are used. As a commercially available product, for example, "PE" manufactured by Tokuyama Corporation
R "and" Cataalloy KS series "manufactured by Montell JPO, which is a reactor alloy type.

The hardness of the olefin-based thermoplastic elastomer resin varies depending on the required feel of the surface of the laminate, but is generally preferably in the range of 50 to 98 in JIS A hardness. Further, in order to improve the extrusion moldability of the olefin-based thermoplastic elastomer resin and the shapeability of the laminate, polypropylene, linear low-density polyethylene (L
LDPE) may be blended.

[0011] The thickness of the substrate layer is 50 to 1,000 µm.
m is preferable, and more preferably, 100 to 700 μm.

If necessary, pigments, light stabilizers, ultraviolet absorbers, heat stabilizers, antistatic agents, fragrances, deodorants, fungicides, and the like may be added to the base material layer.

The adhesive resin layer in the first invention is preferably formed of a polymer or oligomer compatible with a resin used for a skin layer, a base material layer and a foam layer described below, more preferably, It is a polymer or oligomer containing a functional group such as a hydroxyl group, an amide group, an epoxy group, a carboxyl group, a carboxylic acid ester group in the main chain or the side chain.

The polymer containing the above functional group includes:
Acid-modified polyolefin, chlorinated polyolefin,
In addition to ionomer resins (such as metal salts of ethylene-methacrylic acid copolymer), acid-modified SBS (styrene-butadiene-styrene) copolymer, and acid-modified SEBS
(Styrene-ethylene-butylene-styrene) copolymer and the like are themselves elastomeric properties (for example, JIS
(A hardness is about 50 to 98).

The adhesive resin layer which is unlikely to cause the adhesion inhibition by the oil and fat component of the olefin-based thermoplastic elastomer base layer is an acid-modified polyolefin. High polypropylene or high density polyethylene systems may be mentioned.

The thickness of the above-mentioned adhesive resin layer may be a sufficient adhesiveness and a level which does not hinder the formability in forming in a later step, and is preferably 5 to 30 μm. When the adhesive resin layer is formed on both surfaces of the base material layer, the same resin may be used on both surfaces, or different resins may be used.

The adhesive resin layer may be composed of two or more layers, for example, a polyolefin in which the base material layer is acid-modified,
The skin layer side may be formed from nylon or polyester.

As the above-mentioned co-extrusion method, a known method is adopted. Generally, two or more extruders are used, and resins extruded from each extruder are merged into one to form a multilayer. A laminate having the structure can be obtained. As a joining method by co-extrusion, for example, a feed block method, a multi-manifold die method, a multi-throttle die method and the like are used.

In the production method of the first invention, a skin layer is formed on one of the adhesive resin layers formed on the adhesive resin layer side or both surfaces of the co-extruded sheet obtained above, and the skin layer is formed on the adhesive resin layer. Is heat-sealed with a foam made of an olefin-based thermoplastic resin on the surface on the opposite side, and embossing the skin layer.

The skin layer is formed of one or more resins selected from saturated polyesters, acrylic esters and isocyanates. As a method for forming the skin layer, for example, the above resin is dissolved in an organic solvent, and the obtained coating solution is coated with an adhesive resin layer according to a normal coating method (eg, a gravure coating method, an offset coating method, a spray coating method, etc.). A method of applying to the side is adopted.

The side of the adhesive resin layer on which the skin layer is formed may be subjected to corona treatment in advance to improve the adhesiveness.

As the saturated polyester resin, for example, polyethylene terephthalate, polybutylene terephthalate and derivatives thereof are used.

As the acrylate resin, for example, polymethyl methacrylate, polyisobutyl methacrylate, poly-2-ethylhexyl methacrylate and the like are used.

As the isocyanate resin, for example, polyhexamethylene diisocyanate, polyisophorone diisocyanate and the like are used.

In the present invention, a combination of two of the above three resins is preferably used as the skin layer.
Combinations containing all of the species are more preferred for exhibiting surface properties and adhesion.

Examples of the coating solution for the skin layer include “HICOP” manufactured by Nippon Tokusekisho Co., Ltd.
Commercial products marketed by Dainichi Seika are preferably used. The thickness of the skin layer is preferably from 3 to 30 μm, more preferably from 10 to 20 μm.

As the foam, a foam made of a thermoplastic resin is used, for example, a polyolefin resin such as polyethylene or polypropylene; a polystyrene resin such as polystyrene or a styrene-maleic anhydride copolymer; a polyurethane resin A polyvinyl chloride resin; and a foam such as a thermoplastic elastomer resin. In particular, when directly laminating the base material layer and the foam layer, a polyolefin-based resin foam is preferably used, but when laminating via an adhesive resin, the present invention is not limited to this. The foaming ratio of these foams is preferably 5 to 50 times, more preferably 15 to 50 times, in consideration of cushioning properties and soft touch properties.

As a method for heat-sealing the foam, a known method is employed. For example, a skin layer is formed on the adhesive resin layer side of the co-extruded sheet, and then the foam-coated side of the co-extruded sheet is formed. Is heated and melted by a burner or a far-infrared heater, and is passed through a pair of pinch rolls, one of which is an embossing roll, so that the skin layer is preferably embossed simultaneously with the pressure bonding. Also, if necessary,
At the same time as the foam-coated side of the coextruded sheet, the coated surface of the foam itself may be heated and melted.

Further, the foam may be laminated on the adhesive resin layer side of the co-extruded sheet by press molding, and at the same time, the skin layer side may be embossed.

When printing is performed on the laminate obtained by the present invention, a gravure coating method or an offset coating method is used.
A print ink layer may be provided between the adhesive resin layer and the skin layer. The printing ink layer can be formed by using a printing ink solution in which polyvinyl chloride and a pigment; a polyester and a pigment; an acrylic resin and a pigment are dissolved in a solvent such as toluene and methyl ethyl ketone.

Next, the second invention will be described. The method for producing a laminate of the second invention comprises the steps of: forming a foam on one of the adhesive resin layers formed on the base material layer side or both surfaces of the coextruded and molten sheet in the same manner as in the first invention; Heat-sealed and embossed on the unlaminated adhesive resin layer side,
A skin layer is formed on the embossed surface.

As the foam, the same foam as in the first invention is used. The skin layer formed on the embossed surface is obtained by applying at least one selected from a saturated polyester resin, an acrylate resin, and an isocyanate resin, as in the first invention.

As the method for forming the skin layer, the same method as in the first invention is employed, but since the surface to be formed is embossed, the method by spray coating is optimal.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Five types of molten resins were obtained from a 40 mm extruder and a 50 mm extruder (both manufactured by Plastics Engineering Laboratory) using equipment capable of coextruding five layers with three types of resins. The resin is supplied to a feed block (manufactured by Krollen) capable of laminating five layers, and the adhesive resin is adjusted so that it becomes a surface, and introduced into a single mold (manufactured by Krollen) having a width of 500 mm. The obtained molten sheet was cooled by passing through a pair of pinch rolls composed of a metal cooling roll and a rubber roll, and an adhesive resin layer shown in Table 1 was formed on one surface of the base material shown in Table 1, about 400 mm. A coextruded sheet having a width (thickness of the base material layer of 300 μm and thickness of the adhesive resin layer of 10 μm) was obtained.

On the adhesive resin layer side of the coextruded sheet, 6
Using a color printing machine (manufactured by Nakajima Seisakusho), apply 1
80 ° C after coating once with a 20 mesh gravure roll
To form a skin layer. Next, the foam shown in Table 1 was attached to the lower mold of the hot press, and a metal embossed plate was attached to the upper mold. Separately, the co-extruded sheet was cut into a rectangle, and the four sides were clamped by metal fittings, and immediately after being heated by a far-infrared heater so that the surface temperature of the co-extruded sheet was about 140 ° C., immediately attached to the hot press. It was sandwiched between the foam and the embossed plate and press-formed so that the embossed plate was on the skin layer side to obtain a laminate in which the skin layer was embossed.

(Example 2) In the same manner as in Example 1, a rubber roll was laminated in such a manner that the foam shown in Table 1 was laminated on the substrate layer side while coextruding the resin of the substrate layer and the adhesive resin layer. And a pair of pinch rolls composed of a metal cooling roll having an embossed surface, and sandwiching the adhesive resin layer side to the metal roll side to laminate the foam and simultaneously emboss the adhesive resin layer. A processed composite (thickness of the base material layer: 400 μm, thickness of the adhesive resin layer: 15 μm) was obtained. Next, the coating solution for the skin layer shown in Table 1 was spray-coated on the embossed side of the composite, and dried in an oven at 80 ° C. for 3 minutes to obtain a laminate having an embossed pattern on the skin layer.

Example 3 Using a 40 mm extruder, a 50 mm extruder and a 40 mm extruder (all manufactured by Plastics Engineering Laboratory) and the same equipment as in Example 1, both surfaces of the base material layer shown in Table 1 were used. A co-extruded sheet (having a base material layer thickness of 300 μm and a thickness of each adhesive resin layer of 20 μm) on which an adhesive resin layer shown in Table 1 was formed was obtained. Next, a laminate in which the skin layer shown in Table 1 was embossed was obtained in substantially the same manner as in Example 1 except that this co-extruded sheet was used.

Example 4 Using a 40 mm extruder, a 50 mm extruder and a 40 mm extruder (all manufactured by Plastics Engineering Laboratory) and the same equipment as in Example 1, both sides of the base material layer shown in Table 1 were used. Example 3 except that the co-extrusion was carried out so that the adhesive resin layer shown in Table 1 was formed (the thickness of the base material layer was 300 μm, and the thickness of the adhesive resin layer was 20 μm).
A laminate having an embossed pattern on the skin layer shown in Table 1 was obtained in substantially the same manner as in Example 1.

(Comparative Example 1) Only the substrate layer (thickness: 300 μm) was extruded from the same equipment as in Example 1, and then a primer layer was previously formed on one surface of the substrate layer.
A skin layer was formed in the same manner as described above. Next, the foam shown in Table 1 was laminated by the same pressing method as in Example 1, and at the same time, the skin layer side was embossed to obtain a laminate.

(Comparative Example 2) The same procedure as in Example 2 was repeated except that only the substrate layer (thickness: 300 μm) was extruded from the same equipment as in Example 1 and a foam was laminated on one side. Was embossed. Next, after forming a primer layer on this surface in advance, a skin layer was formed by spray coating to obtain a laminate.

The following evaluation was performed on the above-mentioned laminate, and the results are shown in Table 1. (1) Adhesion of skin layer One day after the formation, 11 parallel lines were cut on the surface of the skin layer with a sharp razor at intervals of 2 mm, and further cut at intervals of 2 mm in a direction perpendicular to the cut. The book was scored in parallel lines. These cuts form 100 squares of 2 mm square. Then, a cellophane adhesive tape was stuck so as to cover all the 100 squares, and immediately a vigorous peeling test was performed on the cellophane adhesive tape. Table 1 shows the number of the 100 squares that did not come off. Displayed in.

(2) Adhesion of foam The laminate was peeled from between the foam and the co-extruded sheet.
Were determined to be Δ, and those not exceeding 50% were determined to be ×.

[0044]

[Table 1]

The following components were used in the table. -Base material: 40% by weight of an olefin-based thermoplastic elastomer ("Millastomer 8030N" manufactured by Mitsui Petrochemical Co., Ltd., JIS A hardness: 85) and 40% by weight of an olefin-based thermoplastic elastomer ("Milastomer 5030 manufactured by Mitsui Petrochemical Co., Ltd.")
N ", JISA hardness: 50) 40% by weight of polypropylene and 20% by weight of polypropylene (" F3122 "manufactured by Chisso Corporation) (shown in the table) Adhesive resin: (A) Polypropylene (Mitsui Oil "Admer QF305" manufactured by Chemical Co., MI = 1.5) (B) Polypropylene ("Admer QE800" manufactured by Mitsui Petrochemical Co., MI = 9.1) (C) Acid-modified SEBS ("Toughtec" manufactured by Asahi Kasei Corporation) M1943 ", JIS A hardness: 67)

Foam: (I) polypropylene (“Softlon SPV2502” manufactured by Sekisui Chemical Co., Ltd., expansion ratio: 25 times, thickness 2)
mm) (II) Polyethylene ("Softlon IF" manufactured by Sekisui Chemical Co., Ltd.)
3002 ", expansion ratio: 30 times, thickness 2 mm) (III) Urethane type (soft urethane foam" ECA "manufactured by Inoac Co., expansion ratio: 38 times, thickness 2 mm)

Skin layer: (a) 100 parts by weight of saturated polyester resin + acrylate resin + isocyanate resin (“HICOPE V EK-167” manufactured by Nippon Tokusekisho Co., Ltd. + “HICOPE VUA”
-63 "2 parts by weight) (b) Urethane elastomer (" HI-COP EU-684 "manufactured by Nippon Tokusekisho Co., Ltd.)

Primer layer: polyester resin ("Joytack AD-180" manufactured by Nippon Special Color Co., Ltd.)

[0049]

The method for producing a laminate according to the present invention has the above-described structure, and by providing an adhesive resin layer on at least one surface of the base material layer, the adhesion of the olefin-based thermoplastic elastomer is inhibited by the oils and fats. Since the size can be reduced, a laminate having excellent skin layer adhesion can be provided without requiring a degreasing step or a primer coating step. In addition, the adhesive resin layer can be formed on at least one surface of the base material layer in one step, and even when the foam is different from the olefin resin of the base material, the adhesive resin layer can be easily laminated. .

Continued on the front page (51) Int.Cl. ⁶ Identification code FI B32B 5/18 B32B 5/18 25/08 25/08 27/30 27/30 A 27/36 27/36 27/40 27/40 C08J 7 / 04 C08J 7/04 Z

Claims (2)

[Claims] 1. A co-extrusion of an adhesive resin layer and a base material layer made of an olefin-based thermoplastic elastomer resin so as to form an adhesive resin layer on one or both surfaces of the base material layer. Forming a skin layer by applying at least one selected from a saturated polyester resin, an acrylate resin and an isocyanate resin to one of the adhesive resin layers formed on the adhesive resin layer side or both surfaces of the sheet. A method for producing a laminate, comprising: heat-sealing a foam made of a thermoplastic resin on a surface opposite to the skin layer; and embossing the skin layer side. 2. A molten resin immediately after co-extrusion of an adhesive resin layer and a base material layer made of an olefin-based thermoplastic elastomer resin so as to form an adhesive resin layer on one or both surfaces of the base material layer. Either one of the adhesive resin layers formed on the base material layer side or both surfaces of the extruded sheet is heat-sealed with a foam made of a thermoplastic resin and embossed on the unlaminated adhesive resin layer side, A method for producing a laminate, wherein a skin layer is formed by applying at least one selected from a saturated polyester resin, an acrylate resin and an isocyanate resin onto an embossed surface.